Certain 3-haloacyl-2,2,5-trimethyl-oxazolidines

ABSTRACT

Substituted oxazolidines and thiazolidines having the formula ##SPC1## 
     In which X is oxygen or sulfur; R is haloalkyl, alkyl or alkylthio; and R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are independently selected from the group consisting of hydrogen, lower alkyl, alkoxyalkyl and lower alkylol; provided that when X is oxygen and R is alkyl, then at least one of R 1 , R 2 , R 3 , R 4 , R 5  and R 6  is other than hydrogen. The compounds are active as an antidote against crop injury, when used with various herbicides.

This application is a continuation-in-part of copending application Ser. No. 484,514, filed July 1, 1974 now abandoned, which in turn is a continuation of then copending application Ser. No. 356,548, filed May 2, 1973, now abandoned, which in turn is a continuation-in-part of then copending application Ser. No. 297,582, filed Oct. 13, 1972, now abandoned.

This invention relates to certain novel substituted oxazolidines and thiazolidines which are useful as antidotes against crop injury by various herbicides. The compounds of the present invention are new compositions of matter and correspond to the general formula ##SPC2##

In which X is oxygen or sulfur; R is haloalkyl, alkyl or alkylthio; and R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from the group consisting of hydrogen, lower alkyl, alkoxyalkyl and lower alkylol; provided that when X is oxygen and R is alkyl, then at least one of R₁, R₂, R₃, R₄, R₅ or R₆ is other than hydrogen.

In the above description, the following embodiments are intended for the various substituent groups: For R, haloalkyl and alkyl preferably includes, unless otherwise provided for, those members which contain from 1 to 10 carbon atoms, inclusive, in both straight chain and branched chain configurations, and the term halo includes chloro and bromo as mono, di, tri, tetra and per substitutions. As exemplary of the alkyl portion within the preferred embodiment are the following: Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, 1,1-dimethylbutyl, amyl, isoamyl, 2,4,4-trimethylpentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl, nonyl, and decyl. The term alkylthio preferably includes those members which contain from 1 to 4 carbon atoms, inclusive, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, t-butylthio, and the like. For R₁, R₂, R₃, R₄, R₅ and R₆, the term lower alkyl preferably includes, unless otherwise provided for, those members which contain from 1 to 4 carbon atoms, inclusive, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, and the like. The term alkoxyalkyl preferably includes those members having a total of 2 to 4 carbon atoms, inclusive, for example, methoxymethyl, methoxyethyl, ethoxyethyl, ethoxymethyl and the like. The term lower alkylol preferably includes those members having 1 to 4 carbon atoms, inclusive, for example, methylol, ethylol, propylol and butylol.

PREFERRED EMBODIMENTS OF THE INVENTION

The preferred embodiments of the invention are realized when the following substitutions are present in compounds corresponding to the general formula (I), supra. ##SPC3##

in which X is oxygen, R is selected from the group dichloromethyl, tribromomethyl, trichloromethyl, 1-bromoethyl, monobromomethyl, 1,2,4,4-tetrabromopentyl, 2-chloroethyl, 1,2-dibromoethyl, 2-bromoethyl, ω-bromodecyl, 3-chloropropyl, 2-chloropropyl, 1-bromopropyl, 1-bromobutyl, 5-bromopentyl; R₁ is methyl, R₂ is selected from the group methyl, ethyl, t-butyl, i-propyl; R₃, R₄, R₅ and R₆ are each hydrogen; provided that when R is dichloromethyl, R₂ is other than methyl; ##SPC4##

in which X is oxygen, R is monochloromethyl, R₂ is selected from the group methyl, ethyl, t-butyl, i-propyl; and R₃, R₄, R₅ and R₆ are each hydrogen; ##SPC5##

in which R is haloalkyl having 1 to 10 carbon atoms, inclusive, and halo is selected from chloro and bromo, R₁ is lower alkyl having from 1 to 4 carbon atoms, inclusive, R₂ is lower alkyl having from 1 to 4 carbon atoms, inclusive, and R₃, R₄, R₅ and R₆ are each hydrogen; ##SPC6##

in which R is selected from the group tribromomethyl, monochloromethyl, dichloromethyl, 1-bromoethyl, monobromomethyl, 1,2-dibromoethyl, 2-chloropropyl, 1-bromopropyl, 1-bromobutyl, 3-chloropropyl, 5-bromopentyl; R₁ is methyl, R₂ is methyl, R₅ is methyl and R₃, R₄ and R₆ are each hydrogen; ##SPC7##

in which R is selected from the group consisting of dichloromethyl, trichloromethyl, monobromomethyl, 1-bromoethyl and tribromomethyl, R₁ is methyl, R₂ is methyl, R₃ is methyl and R₄ is methyl, and R₅ and R₆ are each hydrogen; ##SPC8##

in which R is haloalkyl having 1 to 10 carbon atoms, inclusive, halo is selected from chloro and bromo, R₁ is lower alkyl having 1 to 4 carbon atoms, inclusive, R₅ is lower alkyl having from 1 to 4 carbon atoms, inclusive, and R₂, R₃, R₄ and R₆ are each hydrogen; ##SPC9##

in which R is haloalkyl having from 1 to 10 carbon atoms, inclusive, halo is selected from chloro and bromo, R₃ is lower alkyl having from 1 to 4 carbon atoms, inclusive, and R₁, R₂, R₄, R₅ and R₆ are each hydrogen.

(8) Also, N-haloacyl (2-alkylated) oxazolidine wherein the haloacyl group is C₂ ₋₄ acyl, and the 4 and 5 carbon atoms of the oxazolidine ring are satisfied by hydrogen or C₁ ₋₆ alkyl groups.

Some of the compounds of this invention are active herbicides and can be used in herbicidal compositions to control the growth of undesirable vegetation. The compounds also are useful in plant growth regulating compositions, nematocidal, algicidal, bacteriostatic and fungicidal compositions.

Among the many herbicidal compounds commercially available, the thiocarbamates, alone or admixed with other herbicides such as the triazines, have reached a relatively high degree of commercial success. These herbicides are immediately toxic to a large number of weed pests at different concentrations varying with the resistance of the weed pests. Some examples of these compounds are described and claimed in the U.S. Pat. Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,314.

It has been found in practice that the use of these thiocarbamates as herbicides on crops sometimes causes serious injuries to the crop plants. When used in the recommended amounts in the soil to control many broadleaf weeds and grasses, serious malformation and stunting of the crop plants result. This abnormal growth in the crop plants results in loss of crop yield. Previous attempts to overcome this problem involves the treatment of the crop seed with certain antagonistic agents prior to planting, see U.S. Pat. Nos. 3,131,509 and 3,564,768. These antagonistic agents have not been notably successful. The aforementioned patent specifically exemplifies the treatment of seeds employing compounds of a different chemical class not suggestive of the present invention.

Other herbicidal compounds whose effect can be modified by the instant compounds include the acetanilides, such as 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide and the urea-type herbicides, such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

It has been discovered that plants can be protected against injury by thiocarbamate-type herbicides, alone or mixed with other herbicides. An alternative mode of action is for the tolerance of the plants to the active herbicidal compounds to be substantially increased by adding to the soil an antidotally effective amount of a compound described in this invention according to the formula ##SPC10##

in which X, R, R₁, R₂, R₃, R₄, R₅ and R₆ are as defined above.

As an alternative mode of action, the compounds of this invention may interfere with the normal herbicidal action of the thiocarbamate herbicides to render them selective in their action.

Whichever mode of action is operative, the corresponding beneficial and desirable effect is the continued herbicidal effect of the thiocarbamate with the accompanying decreased herbicidal effect on desired crop species. This advantage and utility will become more apparent hereinafter.

Therefore, the terms herbicide, antidote or antidotal amount, is meant to describe that effect which tends to counteract the normal injurious herbicidal response that the herbicide might otherwise produce. Whether it is to be termed a remedy, interferant, protectant, or the like, will depend upon the exact mode of action. The mode of action is varied, but the effect, which is desirable, is the result of the method of treating the soil in which a crop is planted. Hitherto, there have been no systems which have been satisfactory for this purpose.

The compounds of this invention represented by the above formula can be prepared by several different procedures depending upon the starting materials.

The oxazolidine and thiazolidine intermediates are prepared by the condensation of an amino alcohol or mercaptan with a suitable aldehyde or ketone in boiling benzene with the continuous separation of water. This method is described by Bergmann et al., JACS 75 358 (1953). Usually, the oxazolidines and thiazolidines intermediates are pure enough to be used directly without further purification. Aliquots of these solutions are then used to prepare the compounds of this invention.

The appropriate intermediate is reacted with an acid chloride in the presence of a hydrogen chloride acceptor, such as triethylamine, to prepare the desired compound. Workup and purification procedures involve standard methods of extraction, distillation or crystallization.

The compounds of the present invention and their preparation are more particularly illustrated by the following examples. Following the examples of preparation is a table of compounds which are prepared according to the procedures described herein. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

EXAMPLE I Preparation of 2,2-dimethyl-3-dichloroacetyl oxazolidine.

Five and one-tenth grams of 2,2-dimethyl oxazolidine dissolved in 50 ml. of benzene was treated with 5.5 g. of triethylamine and 7.4 g. of dichloroacetyl chloride was added dropwise with stirring and cooling in an ice bath. The mixture was poured into water, the benzene solution separated, dried over anhydrous magnesium sulfate and the solvent stripped under vacuum. The product was a waxy solid which had a melting point of 113°-115°C. on recrystallization from diethyl ether.

EXAMPLE II Preparation of 2,2,5-trimethyl-3-dichloroacetyl oxazolidine.

Eighteen milliliters of a benzene solution containing 4.6 g. of 2,2,5-trimethyl oxazolidine was added to 25 ml. of benzene and 4.5 g. of triethylamine. Five and nine-tenths grams of dichloroacetyl chloride was added dropwise with stirring and cooling in an ice bath. When reaction was complete the mixture was poured into water and the benzene layer separated, dried over anhydrous magnesium sulfate and the benzene removed under vacuum. Yield was 7.7 g. of an oil, n_(D) ³⁰ = 1.4950.

EXAMPLE III Preparation of 2,2-dimethyl-3-dichloroacetyl thiazolidine.

Four and seven-tenths grams of 2,2-dimethyl thiazolidine and 4.5 g. of triethylamine were dissolved in 50 ml. of methylene chloride and 5.9 g. of dichloroacetyl chloride was added dropwise with stirring. The mixture was cooled in a water bath at room temperature.

When reaction was complete, the mixture was poured into water and the solvent layer separated, dried over anhydrous magnesium sulfate, and the solvent removed under vacuum. Yield was 3.6 g. of a waxy solid. Recrystallization of another sample from diethyl ether gave a white solid, m.p. 109°-111°C.

EXAMPLE IV Preparation of 2,2,5-trimethyl-3(2' ,3'-dibromopropionyl)oxazolidine.

Fourteen milliliters of a benzene solution containing 3.5 g. of 2,2,5-trimethyl oxazolidine was added to 25 ml. of benzene and 3.5 g. of triethylamine. Seven and one-half grams of 2,3-dibromopropionyl chloride was added dropwise with stirring and cooling in an ice bath. When reaction was complete, the mixture was poured into water and the benzene layer separated, dried over anhydrous magnesium sulfate and the solvent stripped under vacuum. The yield was 5.7 g. of an oil, n_(D) ³⁰ = 1.5060.

EXAMPLE V Preparation of 2,2-dimethyl-3-dibromoacetyl thiazolidine.

To a mixture of 3.5 g. of 2,2-dimethyl thiazolidine, 50 ml. of benzene and 7.1 g. of dibromoacetyl chloride mixed in an ice bath was added 3.1 g. of triethylamine dropwise with stirring and continued cooling. When reaction was complete, the mixture was poured into water and the benzene layer separated, dried over magnesium sulfate and the benzene removed under vacuum. Yield was 8.5 g. of a dark oil.

EXAMPLE VI Preparation of 2-ethyl-3-S-ethylthiocarbonyl oxazolidine.

Sixteen and one-half milliliters of a benzene solution of 2-ethyl oxazolidine was added to 50 ml. of benzene and 4.1 g. of triethylamine. Five grams of ethyl chlorothiolformate was added dropwise with stirring and cooling in an ice bath. The mixture was poured into water and the benzene solution separated, dried over anhydrous magnesium sulfate and the benzene stripped under vacuum. Yield was 5.6 g. of an oil, n_(D) ³⁰ = 1.5130.

EXAMPLE VII Preparation of 2,2-dimethyl-3-heptanoyl oxazolidine.

Sixteen and one-half milliliters of a benzene solution containing 4.6 g. of 2,2-dimethyl oxazolidine was added to 50 ml. of benzene and 4.1 g. of triethylamine. To this mixture 6 g. of n-heptanoyl chloride was added dropwise with stirring and cooling in an ice bath. The mixture was poured into water and the benzene layer extracted, dried over magnesium sulfate and the benzene removed under vacuum. Yield was 7.5 g. of an oil, n_(D) ³⁰ = 1.4598.

                                      TABLE I                                      __________________________________________________________________________     COMPOUND                                 m.p. °C.                       NUMBER R        R.sub.1                                                                              R.sub.2                                                                            R.sub.3                                                                           R.sub.4                                                                            R.sub.5                                                                            R.sub.6                                                                          X or n.sub.D.sup.30                     __________________________________________________________________________     1      CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 116-118                               2      CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.4932                                3      CBr.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.5560                                4      CBr.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                           H  H   CH.sub.3                                                                           H O Glass                                 5      CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                           H  H   CH.sub.3                                                                           H O 1.4842                                6      CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H  H   CH.sub.3                                                                           H O 1.4950                                7      CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H   H   H O 1.4900                                8      CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H   H   H O 1.4950                                9      CCl.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H   H   H O 1.4970                                10     CBr.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H   H   H O 1.5428                                11     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             CH.sub.3                                                                           H  H   CH.sub.3                                                                           H O 1.4993                                12     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H   H   H O 1.4993                                13     CH.sub.2 Cl                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H  H   H   H O 1.4928                                14     CHCl.sub.2                                                                              CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H  H   H   H O 1.4982                                15     CCl.sub.3                                                                               CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H  H   H   H O 1.5034                                16     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H  H   H   H O 1.5058                                17     CBr.sub.3                                                                               CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H  H   H   H O 95-97                                 18     CH.sub.2 Br                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H  H   H   H O 1.5097                                19     CH.sub.2 Br                                                                             CH.sub.3                                                                             CH.sub.3                                                                           H  H   CH.sub.3                                                                           H O 1.5020                                20     CH.sub.2 Br                                                                             CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H   H   H O 1.5048                                21     CH.sub.3 (CHBr.sub.4                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.5658                                22     CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                           H   H O 1.4843                                23     CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                           H   H O 120-123                               24     CCl.sub.2                                                                               CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                           H   H O 1.5031                                25     CH.sub.2 Br                                                                             CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                           H   H O 1.5116                                26     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                           H   H O 1.5140                                27     CBr.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                           H   H O 1.5610                                28     ClCH.sub.2 CH.sub.2                                                                     CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.4538                                29     CHCl.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   H  H   H   H S 1.5458                                30     CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H S 109-111                               31     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H  H   H   H O 1.5170                                32     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             CH.sub.3                                                                           H  H   CH.sub.3                                                                           H O 1.5060                                33     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H   H   H O 1.5083                                34     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.5178                                35     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             t-C.sub.4 H.sub.9                                                                  H  H   H   H O 1.5165                                36     CHCl.sub.2                                                                              CH.sub.3                                                                             t-C.sub.4 H.sub.9                                                                  H  H   H   H O 1.4949                                37     CBr.sub.3                                                                               CH.sub.3                                                                             t-C.sub.4 H.sub.9                                                                  H  H   H   H O 1.5431                                38     CHCl.sub.2                                                                              H     H   CH.sub.3                                                                          CH.sub.3                                                                           H   H O 1.5033                                39     CHCl.sub.2                                                                              CH.sub.3 OCH.sub.2                                                                   H   H  H   H   H O 1.5132                                40     CHCl.sub.2                                                                              C.sub.3 H.sub.7                                                                      H   H  H   H   H O 1.4988                                41     CHCl.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   H  H   H   H O 1.5126                                42     CHBr.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   H  H   H   H O 1.5750                                43     CBr.sub.3                                                                               C.sub.2 H.sub.5                                                                      H   H  H   H   H O 1.5610                                44     CH.sub.2 Br                                                                             C.sub.2 H.sub.5                                                                      H   H  H   H   H O 1.5200                                45     CH.sub.3 CHBr                                                                           C.sub.2 H.sub.5                                                                      H   H  H   H   H O 1.5140                                46     (CH.sub.3).sub.2 CBr                                                                    C.sub.2 H.sub.5                                                                      H   H  H   H   H O 1.4958                                47     CH.sub.2 BrCHBr                                                                         C.sub.2 H.sub.5                                                                      H   H  H   H   H O 1.5273                                48     CH.sub.2 Cl                                                                             C.sub.2 H.sub.5                                                                      H   H  H   H   H O 1.5020                                49     CHCl.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   H  H   CH.sub.3                                                                           H O 1.4955                                50     CH.sub.2 Cl                                                                             C.sub.2 H.sub.5                                                                      H   H  H   CH.sub.3                                                                           H O 1.4890                                51     CH.sub.2 Br                                                                             C.sub.2 H.sub.5                                                                      H   H  H   CH.sub.3                                                                           H O 1.5064                                52     CHBr.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   H  H   CH.sub.3                                                                           H O Glass                                 53     CBr.sub.3                                                                               C.sub.2 H.sub.5                                                                      H   H  H   CH.sub.3                                                                           H O Glass                                 54     CH.sub.3 CHBr                                                                           C.sub.2 H.sub.5                                                                      H   H  H   CH.sub.3                                                                           H O 1.4978                                55     CH.sub.2 BrCHBr                                                                         C.sub.2 H.sub.5                                                                      H   H  H   CH.sub.3                                                                           H O 1.5138                                56     (CH.sub.3).sub.2 CBr                                                                    C.sub.2 H.sub.5                                                                      H   H  H   CH.sub.3                                                                           H O 1.4851                                57     CHCl.sub.2                                                                              H     H   C.sub.2 H.sub.5                                                                   H   H   H O 1.5030                                58     CHBr.sub.2                                                                              H     H   C.sub.2 H.sub.5                                                                   H   H   H O Dark liquid                           59     CBr.sub.3                                                                               H     H   C.sub.2 H.sub.5                                                                   H   H   H O 1.5531                                60     CH.sub.2 Br                                                                             H     H   C.sub.2 H.sub.5                                                                   H   H   H O 1.5173                                61     CH.sub.3 CHBr                                                                           H     H   C.sub.2 H.sub.5                                                                   H   H   H O 1.5076                                62     (CH.sub.3).sub.2 CBr                                                                    H     H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4852                                63     CH.sub.2 BrCHBr                                                                         H     H   C.sub.2 H.sub.5                                                                   H   H   H O 1.5249                                64     CCl.sub.3                                                                               H     H   C.sub.2 H.sub.5                                                                   H   H   H O 1.5048                                65     CH.sub.2 Cl                                                                             H     H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4998                                66     CHCl.sub.2                                                                              CH.sub.3                                                                             H   H  H   H   H O 1.5112                                67     CCl.sub.3                                                                               CH.sub.3                                                                             H   H  H   H   H O 1.5148                                68     CH.sub.2 Cl                                                                             CH.sub.3                                                                             H   H  H   H   H O 1.5077                                69     CH.sub.2 Br                                                                             CH.sub.3                                                                             H   H  H   H   H O 1.5263                                70     CHBr.sub.2                                                                              CH.sub.3                                                                             H   H  H   H   H O 1.5471                                71     CBr.sub.3                                                                               CH.sub.3                                                                             H   H  H   H   H O Dark liquid                           72     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             H   H  H   H   H O 1.5280                                73     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             H   H  H   H   H O 1.5162                                74     (CH.sub.3).sub.2 CBr                                                                    CH.sub.3                                                                             H   H  H   H   H O 1.5013                                75     CHCl.sub.2                                                                              CH.sub.3                                                                             H   H  H   CH.sub.3                                                                           H O 1.4983                                76     CCl.sub.3                                                                               CH.sub.3                                                                             H   H  H   CH.sub.3                                                                           H O 1.4990                                77     CH.sub.2 Cl                                                                             CH.sub.3                                                                             H   H  H   CH.sub.3                                                                           H O 1.4958                                78     CHBr.sub.2                                                                              CH.sub.3                                                                             H   H  H   CH.sub.3                                                                           H O Dark liquid                           79     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             H   H  H   CH.sub.3                                                                           H O 1.5083                                80     CHBr.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   H  H   H   H S 1.5782                                81     CH.sub.2 BrCHBr                                                                         C.sub.2 H.sub.5                                                                      H   H  H   H   H S 1.5650                                82     CCl.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H S 1.5638                                83     CHBr.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H S Dark liquid                           84     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H S 1.5520                                85     CHCl.sub.2                                                                              H     H   H  H   H   H S 75-77                                 86     CHCl.sub.2                                                                              CH.sub.3                                                                             i-C.sub.3 H.sub.7                                                                  H  H   H   H O 1.4960                                87     CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.2 OH                                                                        H   H O 1.4960                                88     CH.sub.2 BrC(CH.sub.3)Br                                                                C.sub.2 H.sub.5                                                                      H   H  H   H   H O 1.5318                                89     CH.sub.2 BrC(CH.sub.3)Br                                                                C.sub.2 H.sub.5                                                                      H   H  H   CH.sub.3                                                                           H O 1.5225                                90     CH.sub.2 BrC(CH.sub.3)Br                                                                CH.sub.3                                                                             H   H  H   CH.sub.3                                                                           H O 1.5210                                91     CHCl.sub.2                                                                              C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4947                                92     C.sub.2 H.sub.5 S                                                                       H     H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4998                                93     C.sub.2 H.sub.5 S                                                                       CH.sub.3                                                                             H   H  H   CH.sub.3                                                                           H O 1.4965                                94     C.sub.2 H.sub.5 S                                                                       C.sub.2 H.sub.5                                                                      H   H  H   CH.sub.3                                                                           H O 1.4973                                95     C.sub.2 H.sub. 5 S                                                                      C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4928                                96     CCl.sub.3                                                                               C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4937                                97     CH.sub.2 BrCHBr                                                                         C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                   H   H   H O 1.5198                                98     CH.sub.2 BrC(CH.sub.3)Br                                                                C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                   H   H   H O 1.5202                                99     CH.sub.2 BrCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4920                                100    CHCl.sub.2                                                                              CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4960                                101    C.sub.3 H.sub.7 S                                                                       CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4900                                102    i-C.sub.3 H.sub.7 S                                                                     CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4875                                103    CCl.sub.3                                                                               CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4990                                104    CH.sub.2 Br                                                                             CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                   H   H   H O 1.5070                                105    CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                   H   H   H O 1.5168                                106    CH.sub.2 BrC(CH.sub.3)Br                                                                CH.sub.3                                                                             H   C.sub.2 H.sub. 5                                                                  H   H   H O 1.5160                                107    CH.sub.2 BrCH.sub.2                                                                     CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4950                                108    C.sub.4 H.sub.9 S                                                                       CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4928                                109    C.sub.4 H.sub.9 S                                                                       C.sub.2 H.sub.5                                                                      H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4880                                110    CH.sub.3 S                                                                              CH.sub.3                                                                             H   C.sub.2 H.sub.5                                                                   H   H   H O 1.4980                                111    C.sub.6 H.sub.13                                                                        CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.4598                                112    CH.sub.3 S                                                                              CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H   H   H O 1.4913                                113    n-C.sub.3 H.sub.7 S                                                                     CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H   H   H O 1.4858                                114    i-C.sub.3 H.sub.7 S                                                                     CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H   H   H O 1.4828                                115    CH.sub.2 BrCH.sub.2                                                                     CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.4912                                116    CH.sub.2 BrCHBr                                                                         H     H   CH.sub.3                                                                          CH.sub.3                                                                           H   H O 1.5221                                117    CH.sub.2 BrCH.sub.2                                                                     CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H S 1.5263                                118    CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H S 1.5573                                119    CH.sub.2 BrCH.sub.2                                                                     H     H   CH.sub.3                                                                          CH.sub.3                                                                           H   H O 1.4890                                120    CH.sub.2 Br                                                                             H     H   H  H   H   H S 1.6032                                121    CH.sub.3 CHBr                                                                           H     H   H  H   H   H S 1.5720                                122    CH.sub.2 BrCH.sub.2                                                                     H     H   H  H   H   H S 1.5629                                123    CH.sub.2 BrCHBr                                                                         H     H   H  H   H   H S 1.5742                                124    CH.sub.3 C(CH.sub.3)Br                                                                  H     H   H  H   H   H S 1.5420                                125    CH.sub.2 ClCH.sub.2                                                                     H     H   H  H   H   H S 1.5475                                126    BrCH.sub.2 (CH.sub.2).sub.8 CH.sub.2                                                    CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.4898                                127    ClCH.sub.2 CH.sub.2 CH.sub.2                                                            CH.sub.3 CH.sub.3                                                                    H   H  H   H   O 1.4880                                  128    ClCH.sub.2 CH.sub.2 CH.sub.2                                                            CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H S 1.5183                                129    CH.sub.3 CHClCH.sub.2                                                                   CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.4896                                130    CH.sub.3 CHClCH.sub.2                                                                   CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.5115                                131    CH.sub.3 CHClCH.sub.2                                                                   CH.sub.3                                                                             CH.sub.3                                                                           H  H   CH.sub.3                                                                           H O 1.4701                                132    C.sub.2 H.sub.5 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.5020                                133    C.sub.2 H.sub.5 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H S 1.5288                                134    C.sub.2 H.sub.5 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H  H   CH.sub.3                                                                           H O 1.4900                                135    C.sub.3 H.sub.7 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.4972                                136    C.sub.3 H.sub.7 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H S 1.5220                                137    C.sub.3 H.sub.7 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H  H   CH.sub.3                                                                           H O 1.4870                                138    CH.sub.2 ClCH.sub.2 CH.sub.2                                                            CH.sub.3                                                                             CH.sub.3                                                                           H  H   CH.sub.3                                                                           H O 1.4747                                139    CH.sub.2 Br(CH.sub.2).sub.4                                                             CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H O 1.4970                                140    CH.sub.2 Br(CH.sub.2).sub.4                                                             CH.sub.3                                                                             CH.sub.3                                                                           H  H   CH.sub.3                                                                           H O 1.4886                                141    CH.sub.2 Br(CH.sub.2).sub.4                                                             CH.sub.3                                                                             CH.sub.3                                                                           H  H   H   H S 1.5249                                142    CH.sub.2 BrCBr(CH.sub.3)                                                                H     H   H  H   H   H S Semi-solid                            143    CH.sub.2 Cl                                                                             H     H   H  H   H   H S 1.5540                                144    CHCl.sub.2                                                                              CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H  H   H   H S 1.5443                                145    CH.sub.3 CHBr                                                                           CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H  H   H   H S 1.4327                                146    CH.sub.2 BrCH.sub.2                                                                     CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H  H   H   H S 1.4293                                147    CH.sub.2 Cl                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H  H   H   H S 1.5279                                148    CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H  H   n-C.sub.3 H.sub.7                                                                  H O 1.4604                                149    CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                           H  H   n-C.sub.3 H.sub.7                                                                  H O 1.4532                                __________________________________________________________________________

It is clear that the classes of herbicidal agents described and illustrated herein are characterized as effective herbicides exhibiting such activity. The degree of this herbicidal activity varies among specific compounds and among combinations of specific compounds within the classes. Similarly, the degree of activity to some extent varies among the species of plants to which a specific herbicidal compound or combination may be applied. Thus, selection of a specific herbicidal compound or combination to control undesirable plant species readily may be made. Within the present invention are prevention of injury to a desired crop species in the presence of a specific compound or combination may be achieved. The beneficial plant species which can be protected by this method is not intended to be limited by the specific crops employed in the examples.

The herbicidal compounds employed in the utility of this invention are active herbicides of a general type. That is, the members of the classes are herbicidally effective against a wide range of plant species with no discrimination between desirable and undesirable species. The method of controlling vegetation comprises applying an herbicidally effective amount of the hereindescribed herbicidal compounds to the area or plant locus where control is desired.

An herbicide as used herein means a compound which controls or modifies the growth of vegetation or plants. Such controlling or modifying effects include all deviations from natural development; for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. By "plants" it is meant germinant seeds, emerging seedlings, and established vegetation, including the roots and above-ground portions.

The compounds of this invention were employed in effective herbicidal antidote compositions comprising thiocarbamates in combination with antidote compounds described hereinabove. They were tested in the following manner.

Corn Seed Treatment Test

Small flats were filled with Felton loamy sand soil. Soil incorporated herbicides were applied at this time. The soil from each flat was placed into a five-gallon cement mixer where the soil was mixed as the herbicides were applied using a predetermined amount of a stock solution containing 936 mg. of 75.5% active ingredient to 100 ml. of water. One ml. of stock solution was applied to the soil in a volumetric pipet for each pound of herbicide desired. One ml. of stock solution contained 7 mg. of herbicide which equals 1 pound per acre when applied to the soil in the flats. After the herbicide incorporation, the soil was placed back into the flats.

Flats of herbicide-treated and untreated soil were then ready to be planted. A pint sample of soil was removed from each flat and placed next to each flat for later use in covering up the seeds. The soil was leveled and rows one-half inch deep were made for planting seeds. Alternating rows of treated and untreated crop seeds were sown. In each test, six PAG 344T field corn seeds were planted in each row. Rows were approximately 11/2 inches apart in the flat. Seeds were treated by either (1) placing 50 mg. of the antidote compound with 16 grams of corn seed in a suitable container and shaking them until the seeds were uniformly covered with the compound; or (2) preparing a stock solution by dissolving 50 mg. of the antidote compound in 5 ml. of acetone then using 0.5 ml. of the solution to treat 10 g. of corn seed (0.05% w/w). Antidote compounds were also applied as liquid slurries and powders or dusts. In some cases, acetone was used to dissolve powdered or solid compounds so they could be more effectively applied to the seeds.

After the flats were seeded, they were covered with the one pint of soil which had been removed just prior to planting. Flats were placed on greenhouse benches where temperatures ranged from 70°-90°F. Flats were watered by sprinkling as needed to assure good plant growth. Per cent control ratings were taken 2, 3 and 4 weeks after the treatments were applied.

In each test, the herbicide was applied alone, in combination with the seed protectant, and the seed protectant was applied alone to check for phytotoxicity. The untreated adjacent row was employed to observe any beneficial lateral movement of the antidote compound through the soil. The degree of the effect was noted by comparison with the control. The results of these tests were tabulated in Table II.

                  TABLE II                                                         ______________________________________                                         Per Cent Injury to Corn from EPTC*                                             Seed Treatment Test                                                                         Per Cent Injury, 2 weeks                                                         Treated     Untreated                                           COMPOUND       Seed        Seed                                                NUMBER         (0.05% w/w) Adjacent Row                                        ______________________________________                                         1**            5           30                                                  2              70          80                                                  3**            40          60                                                  4              10          50                                                  5              30          60                                                  6              0           0                                                   7              40          55                                                  8              0           15                                                  9              10          55                                                  10             20          60                                                  11             30          50                                                  12             10          40                                                  13             50          70                                                  14             0           20                                                  15             20          50                                                  16             10          55                                                  17             30          50                                                  18             20          50                                                  19             40          50                                                  20             20          60                                                  21             50          50                                                  22             60          60                                                  23             50          60                                                  24             20          60                                                  25             20          70                                                  26             20          60                                                  27             20          60                                                  28             60          70                                                  29             0           5                                                   30             20          5                                                   ______________________________________                                         EPTC 6E Untreated Seed                                                                        --          70                                                                             80       (4 wk.)                                     *=S-ethyl dipropylthiocarbamate 6E: 6 lb./A preplant incorporated              **=Seed treatment 0.01% w/w                                              

With 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide at 2 lb/A. as a seed treatment (0.5%), Compound No. 144 gave 100% protection to sorghum (Milo).

Procedure: Multicrop Antidote Screen

Plastic flats were filled with Felton loamy sand soil. Since a variety of grass and broadleaf crops were used in these tests, EPTAM (EPTC) was incorporated at 1/2 and 5 lb/A, while a constant rate of 5 lb/A of the additive was used. EPTAM (EPTC) and the herbicide additive were applied separately by pipetting measured amounts of the appropriate stock solutions into the soil during incorporation in a 5 gallon rotary cement mixer. Stock solutions for EPTAM were prepared as follows:

A. 1/2 lb/A: 670 mg. of EPTC 6E (75.5% a.i.) was diluted with 500 ml. of deionized water so that 2 ml. equals 1/2 lb/A/plastic flat.

B. 5 lb/A: 6700 mg. of EPTC 6E (75.5%) was diluted with 500 ml. of deionized water so that 2 ml. equals 5 lb/A/plastic flat.

Additive stock solutions were prepared by diluting 102 mg. of technical material with 10 ml. of acetone 1% Tween 20 (polyoxy-ethylene sorbitan monolaurate) so that 2 ml. equals 5 lb/A/flat.

After the soil was treated with both herbicide and additive the soil was transferred from the mixer back into the flat where it was then prepared for seeding. The initial step in preparation was to remove a 1 pint sample of soil from each flat to be retained and used to cover the seeds after planting. The soil was then leveled and rows 1/4 inch deep were made in each flat. Flats treated with 5 lb/A of EPTAM were seeded to DeKalb XL-44 corn (Zea maize), US H9 sugarbeets (Beta vulgare), small seeded gray striped sunflower (Helianthus annus), Acala cotton (Gossypium hirsutum), Brag soybeans (Glycine max) and oilseed rape (Brassica napus). Flats treated with 1/2 lb/A of EPTAM were seeded to red oats (Avena byzantina), R-10 [sorghum] (Sorgum vulgare), Fremont HRS wheat (Triticum aestivum), giant foxtail (Seteria feberii), Calrose rice (Oryza sativa) and Blue Mariate barley (Hordeum vulgare). Seeds were then covered with the pint soil sample removed prior to seeding.

The flats were then placed on greenhouse benches where temperatures were maintained between 70°-90°F. The soil was watered by sprinkling to assure good plant growth.

Injury ratings were taken 2 and 4 weeks after the treatments were applied. Soil treated with EPTAM alone at 1/2 or 5 lb/A was included to provide a basis for determining the amount of injury reduction provided by the herbicide antidotes. The per cent protection of various representative crops is reported in Table III. The per cent protection is determined by a comparison with flats not treated with the candidate antidote.

                  TABLE III                                                        ______________________________________                                         Multicrop Screen Results                                                       Per Cent Protection                                                            COMPOUND Rate of               % Protection                                    NUMBER   EPTC lb/A  Crop       (2 weeks)                                       ______________________________________                                         31       0.5        barley     56                                                                  rice       30                                              32       0.5        barley     56                                                                  rice       30                                                                  corn       100                                             33       0.5        rice       30                                                                  barley     44                                              34       0.5        barley     88                                                       5.0        corn       100                                             35       0.5        barley     44                                                       5.0        corn       100                                             36       5.0        corn       100                                             37       5.0        corn       100                                             38       0.5        barley     88                                                       5.0        corn       100                                                      5.0        sunflower  50                                              39       5.0        corn       100                                                      5.0        sunflower  25                                                       5.0        oilseed rape                                                                              60                                              40       5.0        corn       100                                                      5.0        sunflower  25                                              41       0.5        barley     50                                                       5.0        corn       100   (4 weeks)                                 42       5.0        corn       56    (4 weeks)                                 43       5.0        corn       93    (4 weeks)                                 44       5.0        corn       28    (4 weeks)                                 45       0.5        barley     50                                                       5.0        sunflower  81                                              46       0.5        rice       100   (4 weeks)                                 47       0.5        rice       100   (4 weeks)                                          0.5        barley     75    (4 weeks)                                          5.0        oilseed rape                                                                              68    (4 weeks)                                 48       0.5        barley     25                                                       5.0        sunflower  67    (4 weeks)                                 49       0.5        sorghum    50                                                       0.5        barley     50                                                       5.0        corn       100   (4 weeks)                                 50       5.0        corn       10    (4 weeks)                                 51       5.0        corn       42    (4 weeks)                                 52       5.0        corn       100   (4 weeks)                                 53       0.5        rice       100   (4 weeks)                                          0.5        barley     50    (4 weeks)                                          5.0        corn       70    (4 weeks)                                 54       0.5        barley     50                                                       5.0        corn       100   (4 weeks)                                 55       0.5        wheat      20    (4 weeks)                                          0.5        barley     100   (4 weeks)                                          5.0        corn       93    (4 weeks)                                 56       0.5        sorghum    10    (4 weeks)                                 57       0.5        barley     50                                                       5.0        corn       100   (4 weeks)                                 58       0.5        rice       100   (4 weeks)                                 59       5.0        corn       93    (4 weeks)                                 60       0.5        rice       100   (4 weeks)                                          5.0        corn       42    (4 weeks)                                 61       0.5        sorghum    40    (4 weeks)                                          0.5        barley     75    (4 weeks)                                          5.0        rice       70    (4 weeks)                                 62       5.0        oilseed rape                                                                              65    (4 weeks)                                 63       0.5        barley     75                                              64       5.0        corn       42    (4 weeks)                                 65       5.0        corn       70    (4 weeks)                                 66       5.0        corn       100   (4 weeks)                                 67       5.0        corn       28    (4 weeks)                                 68       0.5        rice       100   (4 weeks)                                          5.0        corn       93    (4 weeks)                                 69       5.0        corn       42    (4 weeks)                                 70       5.0        corn       100   (4 weeks)                                 71       5.0        corn       70    (4 weeks)                                 72       0.5        rice       100   (4 weeks)                                          0.5        barley     50    (4 weeks)                                          5.0        corn       100   (4 weeks)                                 73       5.0        corn       100   (4 weeks)                                 74       5.0        corn       42    (4 weeks)                                 75       0.5        sorghum    71                                                       0.5        wheat      60                                                       5.0        corn       87                                                       5.0        oilseed rape                                                                              71                                              76       5.0        corn       56    (4 weeks)                                 77       5.0        corn       100   (4 weeks)                                          5.0        sugarbeets 28    (4 weeks)                                 78       0.5        rice       100   (4 weeks)                                          5.0        corn       100   (4 weeks)                                          5.0        sunflower  81    (4 weeks)                                 79       0.5        barley     50                                                       5.0        corn       100   (4 weeks)                                          5.0        sunflower  67    (4 weeks)                                 80       5.0        corn       70    (4 weeks)                                          5.0        oilseed rape                                                                              56    (4 weeks)                                 81       0.5        barley     50    (4 weeks)                                          5.0        sunflower  67    (4 weeks)                                 82       5.0        corn       56    (4 weeks)                                 83       0.5        rice       100   (4 weeks)                                 84       0.5        rice       100   (4 weeks)                                          0.5        barley     50    (4 weeks)                                 85       0.5        rice       100   (4 weeks)                                          0.5        barley     75    (4 weeks)                                          5.0        corn       93    (4 weeks)                                 86       0.5        barley     50    (4 weeks)                                          5.0        corn       100   (4 weeks)                                 87       5.0        corn       93    (4 weeks)                                 88       0.5        barley     45                                              89       0.5        wheat      67                                                       5.0        oilseed rape                                                                              75                                              90       0.5        wheat      15                                              91       0.5        sorghum    50                                                       5.0        corn       84                                              92       5.0        oilseed rape                                                                              75                                              93       5.0        oilseed rape                                                                              75                                              94       5.0        oilseed rape                                                                              75                                              95       5.0        oilseed rape                                                                              75                                              96       5.0        corn       80                                              97       0.5        barley     50                                              98       5.0        sunflower  60                                              99       0.5        barley     88                                              100      5.0        corn       100                                             101      5.0        sunflower  100                                             102      5.0        oilseed rape                                                                              50                                              103      0.5        sorghum    30    (4 weeks)                                          5.0        corn       100                                             104      0.5        rice       30    (4 weeks)                                          0.5        sorghum    30    (4 weeks)                                 105      0.5        wheat      30    (4 weeks)                                          0.5        barley     75    (4 weeks)                                 106      5.0        sunflower  20    (4 weeks)                                 107      0.5        wheat      40    (4 weeks)                                          0.5        barley     60    (4 weeks)                                          5.0        corn       100   (4 weeks)                                 108      5.0        oilseed rape                                                                              75                                              109      5.0        oilseed rape                                                                              75                                              110      5.0        oilseed rape                                                                              75                                              111      5.0        sunflower  60                                              112      5.0        oilseed rape                                                                              75                                              113      5.0        oilseed rape                                                                              67                                              114      5.0        oilseed rape                                                                              33                                              115      0.5        barley     70    (4 weeks)                                          5.0        corn       10    (4 weeks)                                 116      0.5        barley     58    (4 weeks)                                          5.0        sunflower  60    (4 weeks)                                          5.0        corn       100   (4 weeks)                                 117      0.5        barley     58    (4 weeks)                                          5.0        corn       100   (4 weeks)                                 118      0.5        barley     58    (4 weeks)                                          5.0        corn       65    (4 weeks)                                 119      0.5        barley     68    (4 weeks)                                          5.0        corn       100   (4 weeks)                                 120      5.0        sunflower  30                                              121      0.5        rice       67    (4 weeks)                                          5.0        oilseed rape                                                                              60    (4 weeks)                                 122      0.5        barley     58    (4 weeks)                                          5.0        corn       100   (4 weeks)                                 123      0.5        rice       44    (4 weeks)                                 124      0.5        rice       67    (4 weeks)                                          0.5        barley     58    (4 weeks)                                 125      0.5        rice       88    (4 weeks)                                 126      0.5        rice       100                                                      0.5        barley     100                                             127      0.5        rice       78                                                       0.5        barley     64                                              128      0.5        rice       78                                                       0.5        barley     57                                                       5.0        oilseed rape                                                                              60                                              129      0.5        rice       78                                                       0.5        barley     43                                                       5.0        sunflower  100                                             130      0.5        rice       100                                                      0.5        barley     43                                                       5.0        oilseed rape                                                                              40                                                       5.0        soybeans   33                                              131      0.5        barley     43                                                       5.0        sunflower  100                                                      5.0        oilseed rape                                                                              80                                                       5.0        soybeans   47                                              132      0.5        rice       78                                                       0.5        oats       50                                                       0.5        barley     57                                                       5.0        oilseed rape                                                                              100                                                      5.0        corn       58                                              133      0.5        barley     57                                                       0.5        oats       40                                                       5.0        sugarbeets 45                                                       5.0        oilseed rape                                                                              100                                             134      0.5        barley     43                                                       5.0        soybeans   33                                                       5.0        oilseed rape                                                                              80                                              135      0.5        oats       60                                                       5.0        corn       100                                                      5.0        oilseed rape                                                                              100                                             136      0.5        rice       55                                                       0.5        barley     57                                                       5.0        corn       100                                                      5.0        oilseed rape                                                                              80                                              137      0.5        barley     43                                                       5.0        sunflower  70                                                       5.0        soybeans   33                                              138      0.5        rice       78                                                       0.5        barley     71                                                       5.0        oilseed rape                                                                              60                                              139      5.0        sunflower  70                                                       5.0        oilseed rape                                                                              60                                              140      5.0        sunflower  100                                                      5.0        oilseed rape                                                                              60                                                       5.0        soybeans   33                                              141      5.0        soybeans   47                                                       5.0        oilseed rape                                                                              60                                              142      0.5        rice       86                                                       0.5        barley     62.5                                            143      0.5        rice       100                                                      0.5        barley     87.5                                            144      0.5        sorghum    100                                                      0.5        rice       86                                                       0.5        barley     100                                                      5.0        corn       100                                             145      0.5        rice       100                                                      0.5        barley     100                                             146      0.5        barley     75                                                       5.0        oilseed rape                                                                              100                                             147      0.5        rice       72                                                       5.0        corn       88                                              148*     1.0        sorghum    80    (4 weeks)                                          5.0        corn       100   (4 weeks)                                 149*     5.0        corn       100   (4 weeks)                                 ______________________________________                                          *Herbicide used VERNAM (S-propyl N,N-dipropylthiocarbamate).             

In-furrow method of application employed to apply antidote compound. Stock solutions used:

1 lb/A: 633 mg. of VERNAM (75% a.i.) was diluted with 500 ml. of deionized water so that 4 ml. applied is equivalent to 1 lb/A per flat.

5 lb/A: 633 mg. of VERNAM (75% a.i.) was diluted with 100 ml. of deionized water so that 4 ml. is equivalent to 5 lb/A per flat.

When used with 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide at 2 lb/A, Compounds No. 1 and 30 at 5 lb/A after 4 weeks gave 100 per cent protection to sorghum. Compound No. 1 also gave 67 per cent protection to wheat.

When used with 3-(3,4-dichlorophenyl)-1,1-dimethylurea at 1 lb/A, Compounds No. 1 and 30 at 5 lb/A each gave 60 per cent protection to cotton; Compound No. 1 also gave 60 per cent protection to corn; and Compound No. 30 gave 43 per cent protection to corn.

The antidote compounds and compositions of the present invention can be used in any convenient form. Thus, the antidote compounds can be formulated into emulsifiable liquids, emulsifiable concentrates, liquid, wettable powder, powders, granular or any other convenient form. In its preferred form, a non-phytotoxic quantity of an herbicidal antidote compound is admixed with a selected herbicide and incorporated into the soil prior to or after planting the seed. It is to be understood, however, that the herbicides can be incorporated into the soil and thereafter the antidote compound can be incorporated into the soil. Moreover, the crop seed itself can be treated with a non-phytotoxic quantity of the compound and planted into the soil which has been treated with herbicides, or untreated with the herbicide and subsequently treated with the herbicide. The addition of the antidote compound does not effect the herbicidal activity of the herbicides.

The amount of antidote compound present can range between about 0.001 to about 30 parts by weight of antidote compound described herein per each part by weight of herbicide. The exact amount of antidote compound will usually be determined on economic ratios for the most effective amount usable. It is understood that a non-phytotoxic quantity of antidote compound will be employed in the herbicidal compositions described herein. 

What is claimed:
 1. A compound having the formula ##SPC11##in which R is selected from the group tribromomethyl, monochloromethyl, dichloromethyl, 1-bromoethyl, monobromomethyl, 1,2-dibromoethyl, 2-chloropropyl, 1-bromopropyl, 1-bromobutyl, 3-chloropropyl, 5-bromopentyl; R₁ is methyl; R₂ is methyl; R₅ is methyl; and R₃, R₄ and R₆ are each hydrogen.
 2. A compound according to claim 1 in which R is tribromomethyl.
 3. A compound according to claim 1 in which R is monochloromethyl.
 4. A compound according to claim 1 in which R is 1-bromoethyl.
 5. A compound according to claim 1 in which R is monobromomethyl.
 6. A compound according to claim 1 in which R is 1,2-dibromoethyl.
 7. A compound according to claim 1 in which R is 2-chloropropyl.
 8. A compound according to claim 1 in which R is 1-bromopropyl.
 9. A compound according to claim 1 in which R is 1-bromobutyl.
 10. A compound according to claim 1 in which R is 3-chloropropyl.
 11. A compound according to claim 1 in which R is 5-bromopentyl.
 12. The compound having the formula ##SPC12##
 13. The compound having the formula ##SPC13## 